CN218596229U - Device for extracting butyl glycolate from organic wastewater - Google Patents

Abstract

The utility model relates to a device for extracting butyl glycolate from organic wastewater, wherein a glycolic acid solution storage tank, an acid storage tank, a normal butanol storage tank and a liquid caustic soda storage tank are respectively connected with an esterification kettle; the liquid phase pipeline of the esterification kettle is connected with a filter press through an esterification kettle transfer pump; the filter press is connected with a butyl glycolate transfer tank and a dilute brine transfer tank in sequence through a filter press material transfer pump. The esterification kettle is connected with an esterification condenser through a gas phase pipeline; the esterification condenser is connected with the esterification oil-water separator, and the esterification oil-water separator is respectively connected with the oil phase receiving tank and the water phase receiving tank; the water phase receiving tank is connected with a water phase transfer pump and then connected with a material inlet of a filter press, and the oil phase receiving tank is connected with an oil phase transfer pump and then connected with a normal butanol storage tank. Adopt the utility model discloses a device need not adopt a large amount of organic solvents to contain the concentrated mother liquor of waste water of glycolic acid, avoids secondary pollution. Does not need to be dried to remove moisture, does not generate new waste, and belongs to a clean production device.

Description

Device for extracting butyl glycolate from organic wastewater

Technical Field

The utility model belongs to pesticide waste water recycle field especially relates to a retrieve device of hydroxyacetate in phenoxyacetic acid class pesticide waste water.

Background

The synthetic process route of phenoxyacetic acid pesticide is all through the condensation process of chloroacetic acid and phenol, and in the process, redundant chloroacetic acid can be hydrolyzed to generate glycolic acid. At present, manufacturers producing phenoxyacetic acid pesticides in China all generate a large amount of wastewater with high COD (mainly glycolic acid generated by hydrolysis of sodium chloroacetate and unreacted 2, 4-dichlorophenol). The treatment of the waste water produces a large amount of high COD solid waste, which not only greatly increases the treatment cost of three wastes, but also pollutes the environment. However, the hydroxyacetate compound is an important fine chemical intermediate and is widely applied to the industries of adhesives, dyeing, spinning and daily chemicals. Therefore, the recovery of the glycolic acid in the phenoxyacetic acid pesticide wastewater is of great significance to phenoxyacetic acid pesticide enterprises, can avoid the generation of a large amount of solid waste, can recover valuable glycolic acid or butyl glycolate, and realizes the purpose of changing waste into valuable.

The existing methods for synthesizing hydroxyacetate mainly comprise two methods: one is that glycolic acid and alcohol generate ester under the catalysis of acid; the other is ester which is produced by the reaction of glycolic acid and halogenated hydrocarbon under alkaline condition and the separation and purification by rectification. The first method has the disadvantages of low conversion rate and low utilization rate of raw materials; the second method has the disadvantages that the used halogenated hydrocarbon is generally higher in price than the corresponding alcohol, at least an equivalent amount of alkali is consumed to promote the reaction, new solid waste is generated, and industrial production is not economical.

Patents CN104910017A and CN104744254A disclose the recovery of hydroxyacetate in phenoxyacetic acid pesticide wastewater by using acidic cation exchange resin as catalyst instead of other acid, which has two disadvantages: firstly, solvents such as dioxane, benzene, toluene, xylene, trimethylbenzene, dichloromethane, chloroform, ethyl acetate, acetonitrile or N, N-dimethylformamide are needed to be used for dissolving the wastewater concentrated mother liquor containing the glycolic acid; secondly, the activity of the used acidic cation exchange resin is gradually reduced in the long-term use process, and the acidic cation exchange resin finally becomes solid waste.

Patent CN104744238A discloses that waste water from the production of phenoxyacetic acid pesticides is concentrated and desalted under the condition of reduced pressure and heating to obtain concentrated mother liquor of waste water containing hydroxyacetic acid; dissolving the concentrated wastewater mother liquor in a solvent, adding a drying agent, drying, centrifuging, cooling, crystallizing to obtain glycolic acid, and finally recrystallizing to obtain the high-purity glycolic acid. This method has two disadvantages: firstly, solvents such as methanol, ethanol, n-butanol, isopropanol, n-pentanol, tert-butanol, tert-pentanol, toluene, xylene, trimethylbenzene, chlorobenzene, dichloromethane, trichloromethane, dichloroethane, acetone, ethyl acetate, butyl acetate, methyl formate, ethyl formate, butyl formate, petroleum ether or n-hexane are required to be used; and secondly, the drying agent is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride, calcium oxide, anhydrous calcium sulfate, phosphorus pentoxide or allochroic silica gel and the like to remove water from the concentrated mother liquor of the wastewater, and the method cannot realize continuous industrial production.

Patent CN103193622A discloses a method for recovering glycolic acid from phenoxyacetic acid pesticide wastewater. According to the method, most of inorganic salt, phenol and phenoxyacetic acid organic impurities can be removed. However, because of the strong water solubility of the phenol and the phenoxyacetic acid organic impurities, the amount of the phenol and the phenoxyacetic acid organic impurities contained in the glycolic acid with the content of more than 70wt% obtained by the extraction and concentration method in the patent cannot be ignored; when the glycolic acid crystal is prepared by acetone or acetic acid extraction, the phenol and phenoxyacetic acid organic impurities have better solubility in the two organic solvents, most of the phenol and phenoxyacetic acid organic impurities enter the organic phase, and the phenol and phenoxyacetic acid organic impurities are difficult to remove when the solvents are removed by concentration, so that the phenol and phenoxyacetic acid organic impurities are more in the glycolic acid crystal. Phenol and phenoxyacetic acid organic impurities exist in more than 70wt% of recovered glycolic acid or glycolic acid crystals, and the quality and the application range of the recovered glycolic acid or glycolic acid crystals are seriously influenced.

Disclosure of Invention

The utility model aims at providing a low recovery cost in order to overcome the defect that above-mentioned prior art exists, recovery efficiency is higher retrieves high-quality butyl glycolate's device in phenoxyacetic acid class pesticide waste water, realizes the continuous stable production of industrialization.

A device for extracting butyl glycolate from organic wastewater, wherein a glycolic acid solution storage tank, an acid storage tank, a normal butanol storage tank and a liquid caustic soda storage tank are respectively connected with an esterification kettle;

the liquid phase pipeline of the esterification kettle is connected with a filter press through an esterification kettle transfer pump;

the filter press is connected with a butyl glycolate transfer tank and a dilute brine transfer tank in sequence through a filter press material transfer pump.

The esterification kettle is connected with an esterification condenser through a gas phase pipeline; the esterification condenser is connected with the esterification oil-water separator, and the esterification oil-water separator is respectively connected with the oil phase receiving tank and the water phase receiving tank;

the water phase receiving tank is connected with a water phase transfer pump and then connected with a material inlet of a filter press, and the oil phase receiving tank is connected with an oil phase transfer pump and then connected with a normal butanol storage tank.

The rotary tank in the dilute brine is connected with the rotary tank for storing the dilute n-butyl alcohol through a dilute n-butyl alcohol transfer pump;

the dilute n-butanol middle storage rotary tank is connected with the distillation still oil-water separator through a dilute n-butanol distillation still condenser;

the distillation still oil-water separator is respectively connected with the dilute n-butanol water phase receiving tank and the dilute n-butanol oil phase receiving tank.

The dilute n-butanol water phase receiving tank is connected with a filter press;

the dilute n-butyl alcohol oil phase receiving tank is connected with an n-butyl alcohol storage tank through a distillation kettle oil phase transfer pump.

Adopt the utility model discloses a process of extracting butyl glycolate in organic waste water that the device goes on has following advantage:

(1) Glycolic acid is not directly extracted, but is converted into ester, the glycolic acid is decomposed at 100 ℃, the glycolic acid is mutually soluble with water, the glycolic acid cannot be purified or concentrated in an evaporation concentration mode, and excessive energy is prevented from being used for water evaporation; in addition, the conversion of glycolic acid into butyl glycolate is quickly realized under a homogeneous catalyst system, the efficient separation of sodium chloride impurities and water-phase materials in the materials is realized, and high-quality butyl glycolate products are obtained by recycling.

(2) Butyl glycolate is separated from the wastewater, the purity of the glycolic acid is high, the treatment problem of the phenoxyacetic acid product wastewater is solved, the national industrial policy requirements are met, the resource utilization of organic matters in the wastewater is realized, good economic benefits are obtained, the environmental protection treatment cost is reduced, and the clean production requirements are met.

(3) Adopt the utility model discloses a device need not adopt a large amount of organic solvents to contain the concentrated mother liquor of waste water of glycolic acid, avoids secondary pollution.

(4) Adopt the utility model discloses a device does not need the drying to get rid of moisture, and no new wastes material produces, belongs to clean production technology.

(5) The pH value is regulated by using hydrochloric acid, and the hydrochloric acid can be used as all acids of the whole reaction system, and a new solid super acid or super base is not introduced to be used as a catalyst, so that the finishing system is a chloride ion system, is preferably discharged out of the system in a sodium chloride form, and is suitable for industrial large-scale production.

(6) 50-70% of water brought by the raw material of the glycolic acid solution is subjected to evaporation and oil-water separation, then is mechanically applied to a filter press for dissolving sodium chloride, and finally is evaporated and extracted by an environment-friendly device and then is recycled for synthesizing the phenoxyacetic acid pesticide in the form of condensed water, so that the water is recycled.

Drawings

FIG. 1 shows a device for extracting butyl glycolate from organic wastewater. The system comprises a glycolic acid solution storage tank, a 2.30% hydrochloric acid storage tank, a 3 n-butanol storage tank, a 4.32% caustic soda liquid storage tank, a 5 glycolic acid solution transfer pump, a 6 hydrochloric acid transfer pump, a 7 n-butanol transfer pump, a 8 liquid caustic transfer pump, a 9 esterification kettle, a 10 esterification kettle transfer pump, a 11 filter press, a 12 esterification condenser, a 13 esterified oil-water separator, a 14 water phase receiving tank, a 15 oil phase receiving tank, a 16 water phase transfer pump, a 17 oil phase transfer pump, a 18 butyl glycolate transfer tank, a 19 dilute brine transfer tank, a 20 filter press material transfer pump, a 21 butyl glycolate transfer pump, a 22 dilute n-butanol transfer pump, a 23 dilute n-butanol distillation kettle, a 24 n-butanol distillation kettle transfer pump, a 25 dilute n-butanol distillation kettle condenser, a 26 distillation kettle oil-water separator, a 27 dilute n-butanol phase receiving tank, a 28 dilute oil phase receiving tank, a 29 distillation kettle water phase transfer pump and a 30 distillation kettle oil phase transfer pump.

Detailed Description

Example 1

A device for extracting butyl glycolate from waste water is characterized in that a glycolic acidsolution storage tank 1, anacid storage tank 2, a normal butanol storage tank 3 and a liquid causticsoda storage tank 4 are respectively connected with an esterification kettle 9; and the connection parts of the glycolic acidsolution storage tank 1, theacid storage tank 2, the n-butyl alcohol storage tank 3, the liquid causticsoda storage tank 4 and the esterification kettle 9 are all provided with transfer pumps, and the devices are respectively a glycolic acid solution transfer pump 5, a hydrochloric acid transfer pump 6, an n-butylalcohol transfer pump 7 and a liquid causticsoda transfer pump 8 in sequence.

A liquid phase pipeline of the esterification kettle 9 is connected with afilter press 11 through an esterificationkettle transfer pump 10;

thefilter press 11 is connected with a butylglycolate transfer tank 18 and a dilutebrine transfer tank 19 in turn through a filter pressmaterial transfer pump 20.

The esterification kettle 9 is connected with anesterification condenser 12 through a gas phase pipeline; theesterification condenser 12 is connected with an esterification oil-water separator 13, and the esterification oil-water separator 13 is respectively connected with an oilphase receiving tank 15 and a waterphase receiving tank 14;

the waterphase receiving tank 14 is connected with a waterphase transfer pump 16 and then respectively connected with afilter press 11 and a material inlet of the esterification kettle 9, and the oilphase receiving tank 15 is connected with an oilphase transfer pump 17 and then connected with the n-butyl alcohol storage tank 3.

The dilutebrine transfer tank 19 is connected with a dilute n-butanol intermediatestorage transfer tank 23 through a dilute n-butanol transfer pump 22;

the dilute n-butanol middlestorage rotary tank 23 is connected with a distillation still oil-water separator 26 through a dilute n-butanol distillation still condenser 25;

the distillation still oil-water separator 26 is connected to a dilute n-butanolphase receiving tank 27 and a dilute n-butanolphase receiving tank 28, respectively.

The dilute n-butanol waterphase receiving tank 27 is connected with thefilter press 11 through a distillation kettle waterphase transfer pump 29;

the dilute n-butanolphase receiving tank 28 is connected to the n-butanol storage tank 3 via a distillation still oilphase transfer pump 30.

Example 2

The following process was carried out using the apparatus of example 1: storing the glycolic acid solution with the volume of 7.8m³ The glycolic acid aqueous solution is pumped into an esterification kettle, and a normal butanol storage tank is filled with 12.5m of normal butanol by a normal butanol transfer pump³ Adding n-butanol into esterification kettle, opening steam valve of esterification kettle, heating, and separating oil from waterWater is separated by a device, and the n-butyl alcohol flows back. Adding 30% hydrochloric acid when the temperature in the kettle reaches 100 ℃ in the heating reflux process, controlling the pH value in the kettle to be 1.23, continuously evaporating n-butanol when the water distribution of the esterification oil-water separator is little or no, continuing to evaporate the n-butanol until the temperature of the kettle is more than 125 ℃, starting n-butanol reflux again, cooling to 50 ℃ after reflux heat preservation for 2 hours, adjusting the pH value to be 1.22, discharging, feeding into a filter press, feeding the esterification solution into a butyl glycolate transfer tank, adding the esterification separated water in a water phase receiving tank into the esterification kettle, adjusting the pH value to be 8.05 by using liquid alkali, adding into the filter press to completely dissolve sodium chloride, and pressing the dissolved sodium chloride solution into a dilute n-butanol storage tank by using nitrogen. Pumping the sodium chloride solution in a dilute n-butyl alcohol storage tank into a dilute n-butyl alcohol distillation kettle by a dilute n-butyl alcohol transfer pump, stopping evaporation when the distillation temperature is 105 ℃, the water separation of an oil-water separator of the dilute n-butyl alcohol distillation kettle is little or no, feeding the oil phase into a dilute n-butyl alcohol oil phase receiving tank, feeding the water phase into a dilute n-butyl alcohol water phase receiving tank, continuously applying the water in the dilute n-butyl alcohol water phase receiving tank for dissolving sodium chloride in a filter press, and pumping the n-butyl alcohol in the dilute n-butyl alcohol oil phase receiving tank into the n-butyl alcohol storage tank for continuous application. 99.2 percent of hydroxyl butyl acetate, 0.03 percent of water, 0.5 percent of butanol, 0.05mg/g of acid value and 0.06 percent of other impurities.

Claims (6)

1. The device for extracting the butyl glycolate from the organic wastewater is characterized in that a glycolic acid solution storage tank (1), an acid storage tank (2), a normal butanol storage tank (3) and a liquid caustic soda storage tank (4) are respectively connected with an esterification kettle (9);

a liquid phase pipeline of the esterification kettle (9) is connected with a filter press (11) through an esterification kettle transfer pump (10);

the filter press (11) is connected with a butyl glycolate transfer tank (18) and a dilute brine transfer tank (19) in turn through a filter press material transfer pump (20).

2. The device for extracting the butyl glycolate from the organic wastewater according to the claim 1, wherein the esterification kettle (9) is connected with the esterification condenser (12) through a gas phase pipeline; the esterification condenser (12) is connected with an esterification oil-water separator (13), and the esterification oil-water separator (13) is respectively connected with an oil phase receiving tank (15) and a water phase receiving tank (14).

3. The apparatus for extracting butyl glycolate from organic waste water according to claim 2,

the water phase receiving tank (14) is connected with a water phase transfer pump (16) and then respectively connected with a filter press (11) and a material inlet of the esterification kettle (9), and the oil phase receiving tank (15) is connected with an oil phase transfer pump (17) and then connected with the n-butanol storage tank (3).

4. The apparatus for extracting butyl glycolate from organic wastewater according to claim 1, wherein the dilute brine storage tank (19) is connected with the dilute n-butanol storage tank (23) through a dilute n-butanol transfer pump (22).

5. The device for extracting the butyl glycolate from the organic wastewater according to the claim 1, wherein the storage and transfer tank (23) for the diluted n-butanol is connected with the distillation still oil-water separator (26) through a condenser (25) of the distillation still for the diluted n-butanol;

the distillation still oil-water separator (26) is respectively connected with a dilute n-butanol water phase receiving tank (27) and a dilute n-butanol oil phase receiving tank (28).

6. The apparatus for extracting butyl glycolate from organic wastewater according to claim 5, wherein the dilute n-butanol water phase receiving tank (27) is connected to a filter press (11);

the dilute n-butanol oil phase receiving tank (28) is connected with the n-butanol storage tank (3) through a distillation still oil phase transfer pump (30).

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